Azo derivatives of sulphones and a method of making the same



atented June 20, 19

UNITED STATES PATENT OFFICE AZO DERIVATIVES OF SULPIIONES AND A METHOD OF MAKING THE SAME I Max Dohrn, Berlin-Charlottenburg, and Otto Laubereau, Berlin-Neukolln, Germany, assignors to Schering Corporation, Bloomfield, N. J., a corporation of New Jersey No Drawing. Application November 28, 1940, So iiglsNo. 367,224. In Germany November ZO,

17 Claims.

Y.R.B oraaNn o o v.12. s 01.1mm

and v Y.R.SO2.R'.X

respectively, wherein:

R and R are the same or different aromatic residues,-

X is a urea residue, and

Y an amino group or a group convertible thereinto.

' low solubility, in water.

We have now found, that this drawback may be avoided by the use of specific urea derivatives of the above indicated formulas, namely of those, in which the group Y, which is a group convertible into an amino group, represents an azo group with an aromatic, specifically an aryl, residue, containing one or several groups capable of forming water-soluble salts. These derivatives are obtained by diazotizing in the usual manner compounds described in the above mentioned application, in which Y indicates an amino group, and coupling the diazo compounds obtained with aromatic compounds capable of coupling, especially with compounds of the naphthalene series, as, for instance, naphthoic acids, naphthol sulphonic acids, and naphthyl amino sulphonic acids, substituted with one, preferably with several groups capable of forming water-soluble salts, for instance with carboxyl, sulpho, amino, and the like groups.

Apart from this way of producing compounds according to the present application by means of coupling, they may also be obtained according to other methods known per se, as they are, for instance, described in the German Letters Patent 607,537, 610,320 and 638,701, for instance, by condensing the starting materials with nitroso compounds of the above mentioned compounds capable of coupling, by reduction of suitable azoxy compounds, or by dehydrogenisation of the corresponding hydrazo compounds.

The following examples serve to illustrate the invention, without, however, limiting the same to them.

Example 1 2 grs. of 4-ureido-4'-amino diphenylsulphone are suspended in 20 cos. of absolute alcohol, and, after adding the calculated amount of concentrated hydrochloric acid, diazotized with the calculated amount. of amyl nitrite. To the diazonium chloride solution obtained a concentrated solution of 2.7 grs. of the sodium salt of lnaphthol-3,6-disulphonic acid is added at 0 C. and thereafter neutralized by adding sodium carbonate. The precipitate, a red powder, is filtered oil by suction and washed'with an alcohol-ethermixture; it represents the disodium salt of the 4- ureido diphenyl sulphone-4,2"-azo-1" naphtho1-3,6"-disulphonic acid, which is purified by recrystallisation from water or dilute alcohol. The salt is soluble in water with neutral reaction.

Example 2 2 grs.-of 4-ureido-4'-amino diphenylsulphone Example 3;

2 grs. of 4-'ureido-4'-amino diphenylsulphone are diazotized as described in Example 1, and 1 I coupled with 1.3 grs. o1 3-hydroxy-2-nap'hthoic acid. After filtration by suction and recrystallisation from dilute alcohol, the sodium salt of the 4 ureido diphenylsulphone 434" azo-3"-hy- 1 droxy-2"-naphthoic acid forms bright red needles, which are soluble in water.

trample 4 products with the urea derivatives of the formula wherein Y is an amino group as they are described in Patent No. 2,328,548. Instead of using naphthalene compounds capable of coupling, as they are employed in the above given examples, one may use other aromatic compounds capable of coupling, provided they contain one or several groups capable of forming water soluble salts. Among them there may be mentioned the following: 1-amino-2-phenol, 2-amino-5-nitrophenol, oand p-amino benzoic acid, o-chloro-m-aminobenzoic acid, salicylic acid, p-amino salicylic acid, p-amino benzene monoand disulphonic acid, pamino benzene sulphonic acid, 1-amino-3-phenolsulphonic acid, i-amino benzene-3,5-carboxylic acid, 4-chloro-3-amino benzene sulphonic acid, p-phenylen-diamine-4-sulphonic acid, phenylendiamine-2,6-disulphonic acid, p-resorcylic acid, 2 amino 1 hydroxy naphthalene, aand pnaphthylamine, 1 naphthylamine 4 sulphonic acid, 2-naphthylamine-3- and G-carboxylic acid, 2-naphthylamine-6- and 7- and S-monosulphonic acid, 1-naphthylamine-4,6- and 4,7- and 4,8-disulphonic acid, 2-naphthylamine-3,6- and 4,8- and 6,8-disulphonic acid, 1-naphthylamine-4,8,8- trisulphonic acid. fl-hydroxy naphthoic acid, 2- naphthol-'l-sulphonlc acid, amino-S-naphthol-lsulphonic acid, 1,8 dihydroxy naphthalene-4- sulphonic acid, 2-naphthol-3,d-disulphonic acid, 1,8-dihydroxy-naphthalene-3,6-disulphonic acid, 1,8 naphthylen diamine 3,6-disulphonic acid. dichloro benzyl 1-amino-8-naphthol-4,6-disulphonic acid, 2-naphthol-3,8,8-trisulphonic acid and others.

Of course, many changes and variations in the solvents used, reacting conditions, reaction temperature and duration, the isolating and puritying methods employed and so forth may be made by those skilled in the art, provided they are used in accordance with the principles set forth in the annexed specification and in the claims annexed hereto.

What we claim is:

1. Process for the preparation of derivatives of sulphones of the general formula z.a.s 01.1mm

o o z .a.'s l-B'.NH

and

wherein:

R and R represent phenyl residues,

x a urea residue, and

z an azo group with a radical of the benzene and naphthalene series, containing at least one group capable of forming water soluble salts, comprising diazotizing sulphones of the general formulas Y.R-8.l.R'-NH co Y.R. s macm/ and Y.R.SO =.R'.X respectively, wherein RR and x have the above R and R represent phenyl residues,

Z an azo group linked to a radical of the benzene and naphthalene series containing a group capable of forming water-soluble salts, and

Z a member of the group consisting of z.R.SOa.R' and hydrogen.

5. Aryl azo derivatives of sulphones of the formula Y'.R.S0z.R'.X wherein R and R. represent phenyl residues,

x a urea residue, and

Y an amino group, the aryl radical .being of the benzene and naphthalene series.

6. Azo derivatives of sulphones of the formula Y'.R.BO|-R'.NH

o0 Y'.R.BOs-R'.NE( wherein R and R represent phenyl residues, and

Y an amino group, the azo group being joined to a radical of the benzene and naphthalene series.

'1. Water soluble salts of derivatives of sulphones of the following formula:

Z.R.SO:.R'.NH.CO.NH.Z' wherein R and R represent phenyl residues,

Z an azo group linked to a radical of the benzene and naphthalene series containing a group capable of forming water-soluble salts, and

Z' a member of the group consisting of 23.5023- and hydrogen.

8. Process as claimed in claim 1, wherein the aryl coupling component is a naphthol sulphonic acid compound.

9. Process as claimed in claim 1, wherein the grey; coupling component is a hydroxy naphthoic 10. Process as claimed in claim 1, wherein the coupling component is a hydroxy naphthalene disulphonic acid compound.

11. Process as claimed in claim 1, wherein the coupling component contains a hydroxy group 2' being a naphthyl radical containing at least and a salt-forming group. I one neutralized salt-forming group.

12. Acompound oi the formula 15. Admemiietn r 121m tile 820,11 consist1 ingpgt 4 -urei opheny p one- "-azo- "-na. x IQ-380m 5 thol-3",6"-disulphonic acid and its disodium salt. wherein R and R represent phenyl radicals. X 16. A member of the group consisting of is a urea residue, and X is a radical of the ben- 4 ureido-dipheny1su1phone-4',3"-azo-2"- h. zene and naphflml n series i in at least tho1-1"-sulphonic acid and its sodium salt.

one neutralized s t-1 s crimp- 17. A member oi the group consisting oi A pound as defined i claim 12, where- 10 4 ureido diphenylsui hone ,4 4',4"-azo-3"-hyinx' is anaphtlwl radical. droxy-2"-naphthoic acid and its sodium salt.

14. A compound of the formula aux DOHRN. x'.N=NO-s oFOmcoma, o'rro LAUBEREAU. 

